Higher molecular weight fluorinecontaining compounds



Patented Sept. 30, 1952 UNITED-- PATENT orricr.

- NoDrawing;' Application January 12, 194 9, I .Serial No. 79,592 V Thisinventionrelatesbroadly toa oneestep process for the conversion ofsaturated polyhalogenated organic compounds into fluorine containingcompounds of higher molecular Weight, and it is more particularlyconcerned withv the conversion of l,1,1;3-polyhalogenated organiccompounds into fluorine-containing compounds of highermolecular'weight.As is well known to those familiar with the art, anhydrous hydrogenfluoride has beenused in substitution reactions involving chlorinatedhydrocarbons. Hydrogen fluoride has been added to olefins and acetylene.Mercuric fluoride has been'allowed to react withpolychlorides,polybromides or polyiodides to..prepare'fluorinecontaining compounds.These latter .reactions, however, have not been accompanied byanincrease in the number of carbon atoms in the products formed thereby. ivMercuric fluoride has, beenreacted with alkyl iodides toobtaincomplexfluorides. Fluorides of mercury have been reacted.withiodine-containing compounds toprepareiodofiuoro compounds. Halogenexchange hasubelen. produced-by reacting-hydrogen fluoride with,polyhalogenated compounds such as benzotrichloride. Y a It is apparentfrom an analysisof this. phase of the prior artthat-the addition ofhydrogen fluoride to, organiclcompounds-or the substitution-of fluorinefor other halogenaiboth by the use of hydrogen fluoride :ormetallicfluoride, is common :under carefully controlled conditions.

These processes, howeverihave never been .ac- ,companied by ,an increasein: molec,u1ar weight I of a saturated halogenated. organic compound, i.e., by an increasein the number of carbon atoms.

" H cola? ns. (01. 260 653,)

' It has nowi been;discoveredthat fluorination and an increase inmolecular weight of a' polyhalogenated, saturated organic compoundcan beaccomplishedby a simple, one-step process.--"It has now bGElTfOlll'ldthat l,1,1,3 -polyhalogenated,

"saturated organic compounds can be converted into fluorine-containingcompounds of higher molecular weight by contacting them' with afluorinating agent, under a pressure sufiicient to keep the reactants inthe liquid phase, and at a temperature sumcient to cause bothfluorination and an increase'in molecular weight.

. Accordingly, it is an'object ofthisinvention to provides. novelfluorine-containing organic compounds; Another object is toprovide aprocess for producing the same which is simple and economical. Aspecific object" is-to provide a one-step process for the conversion of1,1,-1,3-

polyhalogenated, saturated organic compounds into fluorine-containingorganiccompounds of increased carbon chain len'gths and molecularweight. Other objects and advantages of the present invention'willbecomeapparent to those skilled in the art from the following" detaileddescription.

Broadly stated, the'present invention provides a one-step process forthe'conversionof'a 1,1,13- =polyha1ogenated, saturated organic compoundhaving-between about [four and-about thirty carbon 'atomsper moleculeinto; fluorine-containing compounds of increased carbon chain length land molecular weight, which comprises contacting said organic compoundswith alarge excess of a fluorinating and condensing agent,

A study ofv the ,prior art als'ozreveals numerous chemically bonded tothe. product except in very .minor. amounts.

in the liquid phase, and at temperatures sufiicient vtoe'ffectfiuori'nation and'condensation', i. of, at

temperatures varying between about 0- Cpand about 150 0., and,preferably, between about C. and about I -In general, halogenatedutilizable herein are the 1,1,1-,3-polyhalogenated,

saturated 'organic compounds having between about four and about thirtycarbon atoms ,per. molecule and-preferably,between five and eighteencarbon atoms per molecule. The organic compound reactant may be a'1,1,1,3-polyh"alo gen'ated, branched-chain or"; straightach'ain jhydrocarbonj or' itmay contain' an .aryl, an alicyclic, or=-anhetero'cyclio jgroupr' The preferred reactants are the l-,-l-,1,3-polyhalogenated, straight? chain,- saturated hydrocarbons havingbetween I organic compounds .1,1,1,3 tetrabromobutane;

about five and about eighteen carbon atoms per molecule, in which atleast two of the halogen atoms are halogen atoms other than fluorine,and in which the halogen atom in the 3-position is a halogen other thanfluorine. For convenience, the organic compound reactant may berepresented by the formula:

I'M R3 R1( Jo-cxs Y H wherein R1 is an organic radical and, preferably,

a hydrocarbon radical, R2 and R3 are organic.-

radicals or hydrogen atoms, preferably, hydrogen, Y is chlorine,bromine, or iodine, and X is a halogen atom, of which at least two arehalogen atoms other than fluorine. Non-limiting ex-.

amples of the organic compound reactantare 1,1,3trichloro-lfluoropentane; 1,1,1,3-tetraiodobutane; 1,1,1-trichloro 3bromopentane; 1,1 ,1,3-tetrachloro'nonane; 1,1,1,3-tetrachloroundecane;1,1,1,3-tetra-- chlorotridecane; 1,1,1,3-tetrachloroheptadecane;1,1,1,3-tetrachloro-3-phenylpropane; 1,1,1,3-tetrachloro--.3-pyridylpropane; and 1,1,1,3-tetrachloro-3-cyclohexylpropane. As setforth hereinbefore, organic compound reactants containing bromine oriodine instead of chlorine, or in combination with chlorine areutilizable, but they are relatively expensive. Accordingly, thepreferred reactants are the 1,1,1,3-tetrachloro compounds of the typeset forth hereinbefore. These reactants may be prepared in many wayswell known in the art.

The reaction involvedin this inventionis carried out by contactingtheorganic compound reactant with a suitable fluorinating andcondensingagent such as anhydrous hydrogen fluoride,

or anhydrous hydrogen fluoride in combination with a metal oxide ormetal halide or both. The preferred metal oxide is mercuric oxide, and.it, in combination with anhydrous hydrogen-fluoride, is the preferredfluorinat'ing and condensing agent. Howevenhydrogen fluoride may be usedin combination with metallic halides such as mercuric fluoride andmercurous fluoride.

In general, the starting material is treated with a large excess ofanhydrous hydrogen fluoride. By this it is meant ratios from four tothirty moles of anhydrous hydrogen fluoride to one mole of startingmaterial. The large excess is necessary to induce the fluoride to enterinto the reaction as an active reactant and not merelyas a catalyst in acondensation process. The large excess coupled with the other conditionsof the reaction supplies the fluorine for the halogen ex,- change thattakes place.

In some instances, it

will be desirable to add a metallic oxide or fluoe ride or other halideto this reaction mixture. Varying amounts of these oxides or halides maybe added ranging from one or two hundredths-of a per cent, based on theweight of the starting material, to several moles per mole of thestarting material, which amounts,- inthe case of the fluorides,apparently enter into the reaction and furnish fluorine for the halogenexchang'e r e-I action.

The pressure utilized in the reaction should be sufiicient to maintainthereactants a liquid phase. This is accomplished by introducingthereactants into an autoclave, with a, suitable pressure control, equippedwith an efficient stirrer to agitate the reaction mixture and increasethe-re:

action rate. The rate should not'be allowed to the reactants are cooledat the beginning of the reaction. Heat is applied as the reactionprogresses by suitable temperature control of the autoclave andtheamount of heat added is only that necessary to carry out the desiredreactions. The temperatures employed depend on the reactants used andwill generally range from about 0 C. to about 150 C., and, preferably,from about C. to about 120 C. Generally, when mercuric oxide. andhydrogen fluoride are present, temperatures from 70 C. to; 120 C. willbe sufficient to cause the desired reactions, whereas slightly highertemperatures will be necessary when hytemperature reactions. In general,however, the

reactions of the present invention are usually complete within a periodof time varying between about two hours and about fifteen hours.

- The following specific examples are for the purpose of exemplifyingthe process of the present invention and the products obtained thereof.It is'to be strictly understood, however, that the invention is not tobe considered as being limited to the specific organic compoundreactants or fluorinating and condensing agents, or to the operationsand manipulations described in the examples. As will be apparent tothose skilled in the art, a wide variety of other reactants, as setforth hereinbefore, may be used to prepare the fluorine containingcompounds of increased molecular weight contemplated herein.

Ewample 1 Onehundred sixty-one grams (0.5 mole) of C10H21CHClCH2CC13 and227.4 grams (1.05 moles) of mercuric oxide were charged into a stainlesssteel autoclave, which was equipped with an efficient stirrer and wasjacketed for temperature control, While this mixture was cooled bycirculation of a coolant of acetone chilled with solid carbon dioxide,200 grams (10 moles) of anhydrous hydrogen fluoride were slowlyintroduced into the cold, agitated mixture. After the final introductionof hydrogen fluoride, which was completed in one, hourjthe temperaturewas raised to C. during 1 hours time and held there for four hours.After cooling, the reaction mixture was flushed from the autoclave withcarbon tetrachloride and the solids were removed by filtration. Thesolids were extracted several times with carbon tetrachloride and theextract added to the main filtrate product. Vacuum distillation of thecombined organic material led to a residue, the properties of which aredescribed in Run No. 1 in Table I. I

Example 2 =.One hundred grams (0.375 mole) of become too high. L Toavoid too violenta reaction, "It

CsHmCHClCI-IaCCla and 174 .5 (0.80 mole) of mercuric oxide werestirredandcooled to 65 C. in a stainless steel autoclave. At thistemperature 150 grams (7.5 moles) of anhydrous hydrogen fluoride wereslowly introduced into the reaction mixture over 30;minutes time. Afterallthe'hydrogen fluoride was introduced, the reaction mixture was heatedto; C. during 45 minutes and held at that temperaturefor 4 hours. Thereaction. mixture, aftercooling, was run. into ice-ice water and washedseveral times with ice water. :The reaction: mixture .was filteredand-thesolids .ex-

tracted with-carbon 1 tetrachloridej.. All: the :com=

bined organic :material was subjected :to. vacuum distillation to Obtaina' residue,- the piropertiestof which are described as Run No. 2 inTable-I. 3. 11:

' iterate-1' r ots/halide '6 of 131,1,3tetrachlorononane were chargedinto ..a z-liter'zMonel-linedyautoclave and'rapid-ly heated toi99Csatwhich temperature'they'were held'ior 125-ho1'1rs "at;'afmaximum.gaugepressure of 200 pounds per-square inch.- .The .:reactionmixture was discharged .from' the autoclave .intoice-ice water=andthisorg'anicmaterial wasawashed several times with.ice'.-water,iwasdried, filtered and distilled.-. The-residuehas propertiescassummaroled.iz ed' in:Run.No;.51iniTable;I.. 'nie'rcw'ic oxide and hydrogen fluorideiflf' lEl-al'ogen Reactant ....1 .M'ereuri'c Oxide HydrogenTEluoride I 1gimegt -Temi r assist minus g g gg Moles 1 5 1 C1oH21CHO1CHzCC1z 322.15161 .0. 4- 100 266.05 100 0. .I 4 105 378.26 127 o. =.1oo 294, 10 147 0.4 10 265.05 100 0. 12 p "99 H. -H Viscosity-Th1:, I I g j Pressure, ggag 35.33; $223232, Percent {Lfi F WEQ viscosity -lvlfolecular Run No.Grams Number Number I f: v w Besidue' 1 144 1 1a 247 =21.e.- ver 2 105 3so 23.3 3 125 2 61 124 19.1 10.7 4 117 2 5 as 10.4 5 80 2 14 2.2

to 5 C. in a stainless steel autoclave. Two. 35 It will be apparent thata wide variety of fluohundred grams moles) of anhydrous hydrorinatedorganic compounds of high molecular gen fluoride were slowly introducedinto the reweight can be prepared by the process of the action mixtureduring minutes time at -5 present invention. These high-boiling,non-dis- C. After the last hydrogen fluoride introduction, tilledproducts are mixtures of a number of high the temperature was raisedduring minutes 40 molecular weight fluorine-containing compounds. to 100C. and the stirred reaction mixture was The molecular weight valuesindicate that the held at this temperature for 4 hours. After 0001-products contain between about 2 and about, '7 ing, the reaction mixturewas flushed from the times the number of carbon atoms present in theautoclave with carbon tetrachloride into ice-ice saturated halogenatedstarting material. Fluowater. After washing several times with ice 4.5rine and chlorine analyses indicate a variation water, the solids wereremoved from the organic in the relative amount of halogen exchangewhich material by filtration. The solids products were has taken place.Bromine number determinaagain extracted with carbon tetrachloride andtions indicate that some of these final products all organic productscombined, dried, filtered and contain one or more double bonds permolecule. distilled. The properties of the residue obtained Theseproducts have good viscosity indices and are described as Run No. 3 inTable I. relatively low pour points, properties which Example 4 renderthem especially useful as synthetic lubripants. They may also be used ashydraulic fluids Mercuric Oxide, 227,4 grams 05 m d and as additionagents to mineral lubricating oils 147' grams (0.5 mole) of crude1,1,1,3-tetrachloto impart oilin ss p p s and fi m stren th roundecane(CsHrvCHClCHzCCls) were stirred thereto. for the po f eme p essur andchilled to -20 C. At this temperature lubrication 200 grams (10 moles)of anhydrous hydrogen Although the present invention'has been defluoridewere slowly introduced during 15 minscribed in Conjunction W p erredembodiutes. This reaction mixture was then slowly to ments, it is to bunderstood that modifications heated during one hour to 101 C. and heldan variations maybe resorted to without deat that temperature for 4hours. Aftercooling, Parting m the Spirit n cope of this invent reactionmixture was flush d from th tion, as those skilled in the art willreadily underclave with carbon tetrachloride into ice-ice water a d-Such variations and modifications are and washed with ice water severaltimes. The considered to be within the purview and Scope reactionmixture after this treatment was filtered of the appe ded claims. andthe solids were in turn washed with carbon What is claimed is:tetrachloride. All organic material was com- Compounds 0f increasedmolecular W ht; bined, dried, filtered and distilled; Theproperconsisting of the residue obtained by contacting ties of theresulting residue are summarized as a 1,'l,1,3-polyhalogenatedparaffinic hydrocarbon RunN0 4inTab1e 1 having between about 4 and about30 carbon a oms per mo ecu e with a large excess of anh Example 5 g 1drous hydrogen fluoride, in the liquid phase, and Two hundred grams (10moles) of anhydrous at temperatures varying between about 0 C. and about150 C. to produce a reaction product, and

hydrogen fluoride and grams (0.375 mole) removing idistillable matterfrom said reaction product under vacuum distillation conditions. i

2. Compounds of increased molecular weight, consisting of the residueobtained by contacting a 1,1,1,3-polyhalogenated straight chainparaffinic hydrocarbon having between about i and about 30' carbon atomsper molecule wi'tha large excess of'anhydroushydrogen fluoride, initheliquid phase, and at'teniperatures varying between about C. and'abo'ut150 C. to produce a reaction product, and removing distillable matterfrom said" reaction product under vacuum distillation conditions.

3. Compounds of increased molecular weight, consisting of the residueobtained by contacting l,1,1,3-tetrach1orotridecane with a large excessof anhydrous hydrogen fluoride, in the liquid phase. and at temperaturesvarying between about 0 C. and about 150 C. to produce a reactionproduct, and removing distillable matter from said reactions.

4. Compounds of increased molecular weight, consisting of the residueobtained by contacting 1,1,1,3-tetrachloroheptadecane with a largeexcess of anhydrous hydrogen fluoride, in the liquid phase, and attemperatures varying between about 0 C. and about 150 C. to produce areaction product, and removing distillable matter from said reactionproduct under vacuum distillation conditions.

tion produce under vacuum distillation condi-Y tion product under- 5.Compounds of increased moleculariweight, consisting of the residueobtained by contacting 1,1,1,3-tetrachlorononane with a large; excessofanhydrous hydrogen fluoride, in the liquid phase, and at temperaturesvarying between about 0- C. and about C. to producea reaction product,and removing distillable matter from said reacvacuum distillationconditions. c x 6. Compounds 1,1,l,3-tetrachloroundecane with a largeexcess of anhydrous hydrogen fluoride, in the liquid phase,

and at temperatures varying between about 0 C.

REFERENCES CITED The following references are of record in the file ofthis patent:

FOREIGN PATENTS Country Date Great Britain Mar. 22, 1946 OTHERREFERENCES Henne et al., Jour. Am. Chem. 800., vol. 65, pp. 2362-3(1943).

Number of increased molecularweight, consisting of the, residue obtainedby contacting

1. COMPOUNDS OF INCREASED MOLECULAR WEIGHT, CONSISTING OF THE RESIDUEOBTAINED BY CONTACTING A 1,1,1,3-POLYHALOGENATED PARAFFINIC HYDROCARBONHAVING BETWEEN ABOUT 4 AND ABOUT 30 CARBON ATOMS PER MOLECULE WITH ALARGE EXCESS OF ANHYDROUS HYDROGEN FLUORIDE, IN THE LIQUID PHASE, AND ATTEMPERATURES VARYING BETWEEN ABOUT 0* C. AND ABOUT 150* C. TO PRODUCE AREACTION PRODUCT, AND REMOVING DISTILLABLE MATTER FROM SAID REACTIONPRODUCT UNDER VACUUM DISTILLATION CONDITIONS.